ANALYTICAL CHEMISTRY 1

polarography AND METAL ION ANALYSIS

Introduction to polarography Polarography is a type of electroanalytical method used in studying analyte by measuring its current as potential is varied in an electrochemical cell containing the analyte. It is different from

the other voltammetric method in the sense that its electrode is formed by a rhythmically dropping mercury from a tip of fine capillary, while the others have solid electrodes. Polarography is particularly important in quantitative analysis of electroactive species . Trace metal ions(at g/L level or less)in a solution could be analysed. Criteria of polarography  Small sample size(dependent on the type of technique )  Presence of electroactive species (oxidizable or reducible) which are soluble in appropriate liquid solvent which is chemically inert. Dropping Mercury Electrode(DME) which consists of a glass capillary through which mercury flows under gravity to form a succession of mercury drops. It is used to increase the sensitivity of analysis .The mercury surface is altered by the reduced species formed on It(due to discharging). Therefore, the mercury surface is constantly renewed by knocking off the drop of mercury in an interval of time. This causes the data oscillation between maximum and minimum value during data(measured current) recording.(refer figure 1) . This has causing the interpretation of polarogram difficult.(refer figure 2)

 Figure 1: Changes of current with the area, showing the current oscillates
between a near-zero minimum value as drop falls from the capillary to a maximum value as the surface area of a new drop increases.

  

Figure 2: polarogram.The average response is used for subsequent analysis.

Steps in quantitative polarography (1.) Sample treatment: The analyte must be in solution form. Therefore if it is in solid form, it is dissolved in a suitable solvent. Sparingly soluble solid or liquid are to be extracted or digested. In the end of treatment, the solution should be free of suspended solid, colloids and surfactant. (2.) Addition of supporting electrolyte: Examples of supporting electrolyte are salt,acid,base,buffer or chelating reagent. The supporting electrolyte should of high concentration relative to analyte usually at least 10 times the concentration of the analyte. (3.) Bubbling of the solution with N2 This step has to be carried out to remove oxygen. Oxygen always present in solution and it is reducible at the electrode and could interfere with the experimental data. After bubbling , pause a while, the solution is left to quiescent. (4.) Electrode cleaning.

(5.) Scanning/registration of sample polarograms. Instead of keeping the electrode potential(voltage) constant, we do scanning (vary it at time by increase or decrease it). (6.) Addition of the standard analyte. (7.) Scanning/registration of sample polarograms after addition. This step is usually repeated 2 to 8times. (8.) Measurement of all peak/wave heights. The cell potential is measured during the redox reaction at various potentials.

(9.) Drawing of the graphs (polarograms). A current versus potential curve is drawn. (10.) Calculation of the unknown concentration. This is done using formulae. Principle of polarography There are many different polarographic techniques used but the underlying fundamental principle is the same. The electrochemical cell, where the voltammetric experiment is carried out, consists of a working (indicator) Electrode(DME), a reference electrode, and usually a counter (auxiliary) electrode. At the working electrode surface, there is an interface whereby transfer of electron takes place when potential is imposed on it. This interface is called diffusion layer, the poorer concentration of electroactive species in the layer due to its discharging on electrode, creating concentration gradient, results in the mass transport(diffusion) of other electroactive species from bulk solution to the electrode surface and this generates current. This is the current measured by the electrons movement in the external circuit connecting the two electrodes. When an applied potential of about 200 mV is applied to a solution containing only analyte then a very small amount of current will flow to convert a small amount of analyte to reduced form so that Nernst equation is obeyed at the electrode surface. The reduced form(usually metal) would form amalgam with surface mercury of mercury drop.  



   Figure 3. Polarogram with standard reduction potential of analyte. Given E = potential of the working electrode, E = the standard reduction potential of analyte Referring Figure 3: The amount of current rises when the E approached the E, when finally (at B) E = E, [reduced form] = [analyte] at the electrode surface. In other words, at E= E, half of the total analyte reaching the electrode is converted to reduced form, meaning the current is half way to its limiting current. If E is further lowered, all analyte would be reduced as soon as it reaches at the electrode. At C the [analyte] at electrode surface is negligibly small compared to the one of bulk solution. At C the current does not increases linearly with applied potential but approaches a steady limiting value at D which corresponds to the diffusion rate of analyte ions from the bulk solution to the electrode surface.The number of analyte ions diffusing from the bulk solution to the electrode surface is equal to the number that is reduced at diffusion layer, meaning The diffusion rate = reduction rate. 

Figure 3: polarogram and general terms used in polarography Half wave potential (E) is the potential at the point when the current is exactly half of the total current and this value is used to identify the unknown species (qualitative analysis) and limiting current is the difference in the value of the current from the start to the maximum value (that is the sum of migration current, residual current and diffusion current). However, according to Ilkovic equation, keeping all other factors of the equation constant( which corresponds to the elimination of the first two current) the diffusion current (id) which is the wave/peak height is directly proportional to the concentration of the analyte(CA) and this makes quantitative analysis of metal ions possible.

id =KcA
 

K=constant

 As drop forms: (a) At the electrode surface, the concentration polarization occurs and is described by Cottrell equation:

(b)

Area increases with the size of drop.

The effects of (a) and (b) cancel each other out. Combining both equations giving the Ilkovic equation:

 

Quantitative analysis Quantitative analysis is usually done with qualitative analysis. Elimination of the background current Polarographic analysis can be used when concentrations of electroactive species is between 103 to 105 M. If solutions have more than one electroactive species with their E in supporting electrolyte differ by about 0.4 V for single charged ions and 0.2 V for doubly charged ions they can be determined. However, if the E of two ions are close they could be removed by interaction with certain reagents, the common two methods are as followed :

a) precipitation eg. In determination of zinc in Lead and Zinc mixture lead can be removed as lead sulphate precipitate. b) Complexation: Metal ions have complexing ability. By adding complexing agent( e.g. EDTA), E 1/2 of one of the ions may be shifted to more negative potential than the other electroactive species.  The concentration of analyte can be examined only if certain interference is removed. If an analyst prepare a calibration curve using standard solution in distilled water, problems could be encountered if the sample to be analysed has a complex matrix (a matrix rich of general chemical compounds) because these compounds can (i)vary significantly some physical properties of the solution (e.g. viscosity, refraction index etc), or they can (ii)vary the non-specific background instrumental signal or the analyte signal, or, (iii) they could increase or decrease the analytical signal, reacting with the analyte or reagent added to the solution giving rise to the instrumental signal.

One way is to prepare standard solutions in a matrix similar to the samples. Standard addition method is good to avoid matrix interference although cannot compensate the non-specific interference which raise the background signal. Non-specific interference could be solved by measuring the signal as difference between the analytical signal and a background of a blank solution, or, by zeroing the signal with an appropriate blank solution. Methods in Quantitative analysis The two methods usually employed are (i)standard addition method and (ii)internal standard method. The former is the best method for lowering the matrix interference. When the sample matrix is very simple or reproducible the other method called calibration curve method is used.

(i)Internal standard method This is a method to improve the precision of quantitative analysis. An internal standard is actually a substance (with known concentration) which is present in every analyzed sample .It is present in a constant amount in samples, blank and calibration standards. Internal standards are usually used with the calibration curve. Calibration curve is prepared by plotting the ratio of the analyte signal to the internal standard signal versus analyte concentration of the standards. This is done to correct for the loss of analyte during preparation of sample . Internal standard behaves similarly to the analyte but still it provides a signal that can be differentiated from that of the analyte. In other words, factors affecting the analyte signal would affect the internal standard signal to a more or less same degree. Therefore, the ratio of the its signals will has less variability than the analyte signal. Also, standard must have a wave before or after the unknown and the wave must be displaced enough for the two limiting currents to be determined.

Polarogram (currentvoltage curve) of the unknown solution in a supporting electrolyte is recorded. A known amount of standard ion is added into the same solution and polarogram is recorded. (As mentioned before, the only condition is that E 1/2 of standard ion and unknown should be differed by 0.4 V.) In other words, to determine K, a known mixture of standard and analyte (Ck & Cu ) is prepared to measure the relative signals ((id)k & (id)u )of the two species.

  (k=known; u=unknown)  The known amount of internal standard is added to every sample to be analysed and polarogram is analysed. (ii) standard addition method With any kind of the analytical method is used, the interference affects has to be removed, avoiding analytical errors. The best method to avoid some matrix interference is the standard addition method although cannot compensate the non-specific interference which raise the background signal. The only valid strategy to compensate this kind of interference is (i) to measure the signal as difference between the analytical signal and a background signal of a blank solution, or(ii) to zero the signal with an appropriate blank solution. Conditions for the use of the standard addition in Voltammetry is (i)to make the scanning related to each addition using the same parameters to be considered so as to keep the proportionality between concentration and peak height among different scannings constant. (ii) to work in the linear range of the relation between concentration and peak height. In some cases, this range is very narrow. In this case the standard is the same compound as the unknown.

Firstly, the polarogram of the unknown is recorded. Measure (id)u at some potential { (id)u = K .Cu } 

Then, a known amount of standard solution of the same ion (i.e.standard Cs & Vs) is added and a second polarogram is taken. (id)mix is measured under the same conditions.

Cu=concentration of unknown Vu=Volume of the unknown started with Cs=concentration of the standard solution Vs=Volume of standard added   Two equations with two unknowns is obtained, therefore solve for K and Cu    

Experimental Set-up of polarography :

The polarographic circuit:

References: 1) Protti P. (2001). Amel electrochemistry: Introduction to Modern Voltammetric and Polarographic Analisys Techniques. Retrieved 21 November, 2011, from http://www.amelchem.com/download/items/voltammetry/manuals/e ng/manual_eng.pdf 2) UNIT 7: VOLTAMMETRY. Retrieved 21 November, 2011, from vedyadhara.ignou.ac.in/wiki/images/c/ca/Unit_07Voltammetry.pdf 3) UNIT 8: POLAROGRAPHY AND AMPEROMETRIC TITRATIONS. Retrieved 21 November, 2011, from http://vedyadhara.ignou.ac.in/wiki/images/5/58/UNIT_8_POLAR OGRAPHY_AND_AMPEROMETRIC_TITRATIONS.pdf 4) Practical Exercises in Physical Chemistry Advanced Level. Retrieved 21 November, 2011, from pcprakt.userpage.fuberlin.de/SKRIPT/rastertunnel.pdf 5) CHAPTER 1 POLAROGRAPHY. Retrieved 21 November, 2011, from www.newagepublishers.com/samplechapter/001166.pdf 6) Electroanalytical Chemistry, Retrieved 21 November, 2011, from faculty.uml.edu/David_Ryan/84.../ElectrochemLecture102005.pdf 7) Instrumental Methods, Retrieved 21 November, 2011, from http://chemistry.olivet.edu/classes/chem301/pdf/Instrumental%20S ection.PDF